Process of producing crystallized metallic lead plates



(No Model.) 3 Sheets-Sheet l. C. PAYEN.

PROCESS 0E PEODUG'ING SRYSTALLIZED METALLIC LEAD PLATES. No. 440,277.Patented Nov. 11, 1890.

TNEESES. |NVENT|JR= M M (No Model.) 3 Sheets-Sheet 2.

C. PAYEN.

WITNESSEE; lNvlzN'rnRt (No Model.)

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3 Sheets-Sheet 3.

PROCESS OEPEODUGING GEYSTALLIZED METALLIC LEAD PLATES.

Patented Nov. 11, 1890.

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UNITED STATESl PATENT Frrcn.

CLMENT PAYEN, OF PHILADELPHIA, PENNSYLVANIA, ASSIGNOR TO THE vELECTRICSTORAGE BATTERY COMPANY, OF GLOUCESTER CITY, NEIV JERSEY.

PROCESS 0F PRODUCING CRYSTALLIZED METALLIC LEAD PLATES.

SPECIFICATION forming part of Letters Patent No. 440,277, dated November1 1, 1890. Application led January 16, 1888. Renewed April 4, 1889.Serial No. 306,029. (No model.)

To all whom. it may concern,.-

Be it known that I, CLMENT PAYEN, a citizen of the Republic of France,but now residing at the city of Philadelphia., in the count-y ofPhiladelphia and State of Pennsylvania, have invented a certain new andImproved Process for the Production of Crystallized Metal Lead Plates,of which the following is a specification.

My invention relates to the production of porous crystallized metal leadplates.

The invention consists, essentially, in fusing with a charge ol'chloride of lead a varying quantity or percentage of chloride ofcadmium, then discharging the liquid or molten mass into a mold in whichin cooling it assumes a crystallized form, and then reducing the same toa metallic state, whereby'a porous crystallized metal lead structure isproduced having substantial strength.

In the accompanying drawings I have illustrated apparatus suitable forthe conduct of my method of producing crystallized lead plates in suchforms, respectively, as I have found practically ecient, and in which-Figure l is a vertical central section through a melting or fusingfurnace of my improved construction, showing the crucible pivotallysupported therein and operated by a lever for discharging the contentsthereof. Fig. 2 is a top or plan view of a mold made in two sectionshinged to each other, and showing also the means for clamping thesections together. Fig. 3 is an end view of the mold constructed in twosections with the means for clamping the same together. Fig. 4 is aperspective View of a mold made in two sections hinged to each other,and showing also the interior formation thereof. Fig. 5 is a perspectiveView of a bivalved mold for framing the crystallized metal plates. Fig.6 is an end view thereof. Fig. 7 is a top or plan view of saidframing-mold and the clamping device thereof; and Figs. 8 and 9 arediagrammatic views showing the first and second electrolytic actions towhich the crystallized plates are subjected in order to bring them to ametallic state.

Referring to the accompanying drawings, A is thefurnace, constructed ofbrick or other material.

B is the grate located and supported in the lower part of the furnace.

D is the drafttine leading to the chimney D.

E is an arch, made of brick or other refractory material, in the upperpart of the furnace, which is supported in position on a metallic platee, with a central opening therein. The plate e is held in position bymeans of columns f, arranged and supported in the brickwork of thefurnace in any suitable manner.

F is a porcelain erucible or melting-pot open at the top, and around theouter circumference of which is formed a layer cl of amianthus,asbestus,`or other similar material, and

between this layer CZ and the metallic pot F is a film or layer of sandf of any desired. thickness. This metallic capsule or pot F is pivotallysupported in a central position Within the furnace, and is operated fromthe outside by a lever f2, attached to one of the journals of themetallic pot, whereby the crucible F may be readily tilted fordischarging the contents into a receptacle for further treatment.

H is an inclined hopper provided with a removable stopper h, whichpermits of the charging of the salts of the metals or other materialinto the Crucible F.

I is a sliding door, operated in any suitable manner to allow of thedischarge of the liquid or molten mass or compound into a suitable moldfor causing the same to assume a crystallized form.

Having described and pointed out the characteristic features of asuitable melting or fusing furnace, I will now proceed to describe thefirst. step in the process of producing a crystallized metal lead plateof a given sizesay from six to eight inches square. I take for the baseof the charge chloride of lead, and to which I add two per cent., byweight, more or less, of chloride of cadmium, and I prefer to add thechloride of cadmium before fusing the mass; still it may be added to thechloride of lead while in a state of fusion iny the crucible F, it' sodesired. The proportion of chloride of cadmium to the chloride of leadwill in each case depend upon the degree of porosity desired in thefinished plate. It will vthus be observed that by simply varying the IODproportions of the chloride or cadmium to the charge of chloride of leadthedegreeof porosity required may be readily obtained. I have found bypractical experience when a maximum degree of porosity is desired thatthe addition of a third chloride to the mass either before or during thefusing step of the process gives excellent results. The third chloridemay be one of any of the metals which of itself is not of a deliquescentnature and such as will conduce in conjunction with the chloride ofcadmium and chloride of lead to give consistency and strength to thetinished plate, and one which when fused will not be subject toebullition and continue in such condition while being discharged intothe crystallizing-mold, as this would be apt to produce air-bubblestherein and impair to some extent the strength of the structure wh enformed. I have found that the simple addition of chloride of cadmium tothe lead chloride enables me to obtain a crystallized plate which is nothygroscopic, and this is a very necessary condition, especially when itis desired to form a lead frame around the plate for the purpose ofobtainingagood contact in the electrolysis. After the charge composed ofthe chlorides of lead and cadmium has been subjected to fusion in thecrucible F and the mass or compound has reached a liquid state therein,the crucible is tilted by means of the lever f2, and the sliding doorIat the same time raised sufficiently to permit of the discharge of themolten or liquid mass or compound into the mold M through the mouth onthereof.

The selection of proper material for the mold M is of some considerableimportance. The character of the interior surface of the mold islikewise important, and should be perfectly smooth. I have found thatthe best mold is that made of either brass or bronze. Molds made ofmalleable iron or cast-iron become deteriorated in a short time by use,while in the use of those made of iron the chloride of lead is apt toadhere to the sides thereof. The same objection has been found to theuse of porcelain molds. Those made of lead require the exercise of carein use, owing to the tendency of the metal to melt, yet, nevertheless,good results may be obtained by the use of lead ones with care in thehandling of them. The mold to which I give preference is one made ofeither brass or bronze and composed of two symmetrical sections m andm2, chamfered, as shown, for instance, in Fig. 4, and the two sectionsunited to each other by means of hinges m3, held together by\ means ofcatches or pawls m6, secured to the extremities of the shaft m5, whichis held in bearings m7, formed with one of the sections. These pawls orcatches are operated by a lever m4, as shown, for instance, in Figs. 2and 3. The two sections forming the crystallizing-mold M may be formedso that each will be of a uniform thickness of metal, and the thicknessof each section varying from two to ve millimeters, according to thedimensions of' the crystallized metallic' plates to be formed. Thissimilarity and uniform thickness of each section is for some purposesadvantageous, for the reason that crystallization therein commences fromeach side of the mold, and therefore if the two sections are of equalthickness the cooling-point of each will be attained at the same timeand the crystals forming in the mass will meet in the middle. The lineof cleavage of the crystals will therefore be the same throughout theentire crystallized plate, substantially in parallel columns.

I have found that while it is preferable to have the two sections of themold of equal thickness, yet at the same time it is not absolutelynecessary; but when they are not of equal thickness of metal the coolingoff of the material discharged into the same will be unequal, and as aconsequence the line of meeting of the crystals will be more to one sideof the mold than to the other, which may be advantageous in someinstances.

When the molten or liquid mass or compound from the crucible F has beendischarged into the casting-mold M, in a few minutes thereaftersolidiflcation will take place in the cooling o of the same therein,andthe plate cast or formed will become cystallzed. In some instances itmaybe well to heat the mold M previaus to charging the molten or liquidmass or compound into the same-say to a temperature of 150 centigrade,more or lessand thereby obtain good results in the crystallization ofthe plate. /Vhen the plate crystallized has become solid to a greater orless degree, the sections of the mold are unclamped, and the plate thenremoved into a mold N for casting around the crystallized plate a frameof lead or other suitable material.

The bivalved framing-mold N consists of two sections n and n', made ofcast-iron or other suitable material. The section n of the framing-moldN has an upper flange n2 around the sides thereof when in the form of arect- IOO IIO

angular parallelopipedon and with a beveled i flange or rim n3 formed onthe four interior sides of the bottom. With the section lnis formed afunnel-shaped trough or neck n4 for the introduction of material intothe mold when the two sections 'n and n are clamped together by means ofthe pawls or catches a5 and n, rigidly secured to each end of the shaftm7, which is jou rnaledin bearings a8 and n.9, secured to the exteriorsurface of the section a. These pawls or catches are operated by a levern10, which causes the pawls or catches ns and "a9 to engage with thestrengthening-strip nu, formed with or secured to the exterior surfaceof the section n. The section n has an interior beveled rim nu,corresponding with the beveled rim n3 of the section n. The four sidesor edges of the sections n are slightly deflected downward, and a seriesof niches or grooves 'm13 are formed in the under edges, constitutingair-holes when the two sections are clamped together. In the section n',as shown in Fig. 7, two or more openings nl* are formed at suitabledistances apart for the introduction of small pins for holding thecrystallized plate in proper position in the mold to allow lead or othersuitable material to become cast around the plate in the form,preferably, of a beveled frame, with a tongue or support 11,15, for apurpose to be presently described.

The manner of casting a frame around the crystallized plate will now beexplained. The crystallized plate, having been removed from the mold Mto the framing-mold N, is placed in the center thereof, so that thebeveled rim of the mold will be in close proximity to the four sides ofthe rectangular-shaped plate, and in this form the section n of the moldis laid upon the same, so as to occupy the position shown in Fig. 7, andthe two sections clamped together by means of the lever n10. Pins arenow inserted through the small openings n in the section n', in ordertohold the crystallized plate firmly in position. The mold is thenelevated and the liquid or molten lead poured in through thefunnel-shaped trough n4, passing around the crystallized plate and incooling off becoming solidly affixed to or cast around the four sides ofthe crystallized-plate in the form of a beveled frame or border.

IVhen the frame around the sides of the crystallized plate has becomeperfectly solid, the plate may then be removed from the mold, ready forfurther treatment or reduction to a metallic state or condition byelectrolysis or chemical actions, in the following manner: Thecrystallized plate formed in the mold N is now placed in a glasscanister or other receptacle G, containing water and ten per cent. (moreor less) of sulphuric acid, the crystallized plates 2 being immersed inthe solution in the glass canister G and alternated with plates of equaldimension of ordinary lead or articial charcoal 3, each having a tonguex, all the crystallized plates 2 being connected through their tonguesor supports 07,15 with a wire 4, while the lead or charcoal plates 3 areconnected through their tongues 00 with a wire 5, and the two systems ofplates insulated from each other by means of the insulatingrods r, madeof rubber or other suitable material, and from the canister G by meansof the glass insulators 7", mounted on the horizontal bars r2, made ofrubber or other suitable insulating material, in the bottom of the glasscanister G, as shown, for instance, in Fig. S, the system ofcrystallized plates being connected or united to the negative electrodes of the dynamo S, while the system of lead or charcoal plates areunited to the positive electrode 'n16 of the dynamo S, and inconsequence of the electrolytic action which takes place the oxygen andchlorine are separated and caused to attack the system of lead orcharcoal plates, while on the system of crystallized plates remain leadand cadmium metallic. The crystallized plates thus treated are thenremoved and immersed in another glass cannister or receptacle G',containing water and sulphuric acid in about the same proportions ashereinbefore mentioned. In this second receptacle G the crystallizedplates are again alternated with others of ordinary lead or artificialcharcoal, as in the previousinstance, and the two systems of plates,insulated, respectively, from each other and the glass canister G', areagain united by two separate wires 6 and 7, connected with va dynamo S',as in the iirst instance described, with this exception that thenegative electrode s is connected with the system of lead or charcoalplates through the tongues Qc, while the positive electrode m17 isconnected with the system of crystallized plates through the tongue w15,as shown. in Fig. 9. By this second electrolytic action which takesplace the cadmium metallic is deposited on the lead or charcoal platesand the hydrogen escapes and the oxygen is caused to attack thecrystallized plates. The second electrolytio action having beenpermitted to take place, the crystallized lead plates may then beremoved from the canister or receptacle G and thoroughly washed anddried in any suitable manner for such uses as required.

It will be found that crystallized metal lead plates produced by thismethod of treatment with the desired degree of porosity will have aswell great consistency and rigidity and may be made of any form ordimension for electrical accumulators and other purposes.

Having thus described the nature and objects of my invention, what Iclaim as new, and desire to secure by Letters Patent, is

1. The method for the manufacture of a porous crystallized lead plate orother structure, which consists in subjecting the salts of lead andcadmium to fusion, then casting the mass in a mold and allowing it tocrystallize therein, and then reducing the same to a metallic state,substantially as and for the purposes set forth.

2. The method for the manufacture of a porous crystallized metal leadplate, which consists in subjecting the chlorides of lead and cadmium tofusion, then casting the mass in a mold and allowing it to cool andcrystallize therein, and then reducing the same to a metallic state byelectrolytic action, substantially as and for the purposes set forth.

In witness whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

CLEMENT PAYEN. Witnesses: v

J. WALTER DOUG-nnss, HERMANN BORMANN.

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